US8425789B2 - Method and apparatus for anisotropic etching - Google Patents
Method and apparatus for anisotropic etching Download PDFInfo
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- US8425789B2 US8425789B2 US12/587,078 US58707809A US8425789B2 US 8425789 B2 US8425789 B2 US 8425789B2 US 58707809 A US58707809 A US 58707809A US 8425789 B2 US8425789 B2 US 8425789B2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- VIFIHLXNOOCGLJ-UHFFFAOYSA-N trichloro(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC[Si](Cl)(Cl)Cl VIFIHLXNOOCGLJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
Definitions
- This invention relates to a method for etching a substrate in an anisotropic manner.
- the method and apparatus relate to anisotropic etching of nanosize features with high aspect ratios in a substrate.
- a method of anisotropic etching of silicon by cyclic etch and deposition steps in a plasma environment is known as “Bosch process” from German patent DE4241045, issued 5 Dec. 1992 and U.S. Pat. No. 5,501,893, issued 26 Mar. 1996, titled “Method of anisotropically etching silicon”.
- This anisotropic plasma etching has been applied to other materials such as Ge, SiGe and GasAs.
- the model predicts that the critical aspect ratio is defined by the aspect ratio at which the polymer etch rate equals the product of the deposition rate and the set time ratio between the deposition and etching phases for the time-multiplexed process.
- DRIE experiments were performed to qualitatively validate the model. Both model simulations and experimental results demonstrate that the magnitude of the critical aspect ratio primarily depends on (i) the relative flux of neutral species at the trench opening, i.e., the microloading effect, and (ii) aspect ratio dependent transport of ions during the polymer etching subprocess of a DRIE cycle.
- the Si—OH groups bridge and form layers of oxide.
- the oxide continues to grow due to field assisted Mott-Cabrera mechanism.
- the fluorine-enhanced oxide layer postpones the attack of the sidewalls during the following brief plasma etching.
- the sidewall passivation is thus enabled. Obviously, control of sidewall passivation layer thickness and uniformity is very problematic with this method.
- Suk Won Yu has used dielectric etch preventing spacer deposited on the sidewall of the etched feature in KR 10-2006-0030717. Unfortunately, due to the chosen deposition method such spacer is quite thick and non-uniform along the length of the sidewall feature, as it clearly seen from the patent's text and the drawing. Mr. Yu does not teach how to get uniformly deposited sidewall passivation layer, which will be thin enough and uniform enough for nano-sized features with high aspect ratio.
- such sidewall passivation layer is a Self-assembled monolayer (SAM) material deposited in-situ etching process from a vapor phase.
- SAM Self-assembled monolayer
- such sidewall passivation layer is an inorganic-based material deposited using Atomic Layer Deposition (ALD) method.
- ALD Atomic Layer Deposition
- SAM or ALD layers deposition can be carried out in a pulsing regime alternating with an etching or sputtering processes using process gasses with or without plasma.
- a SAM deposition process is carried out continuously, while an etch or sputtering process turns on in a pulsing regime.
- a SAM deposition process and etch or sputtering processes are carried out continuously.
- Both types of suggested passivation materials give advantages over state-of-the-art methods in ability to carefully control thickness and uniformity of the layers, and thus enable extending achievable high aspect ratio and narrow nanosize feature anisotropic etching process.
- FIG. 1 shows a schematic representation of Self-assembled Monolayer (SAM). Deposition of these layers is self-limiting (deposition stops when entire surface is filled with one layer of molecules), thus thickness of this layer is always equal to the one molecular length (practical thickness range is 0.5-3 nm) and uniformity of deposited layer is 100%.
- SAM Self-assembled Monolayer
- FIG. 2 is a schematic which shows the status after the SAM or ALD-material deposition step: substrate 1 is covered with patterned photoresist 2 , and then SAM or ALD-material layer 3 deposited on top of both, photoresist 4 and exposed substrate material 5 .
- FIG. 3 is a schematic which shows the status after the first etching or sputtering step: SAM or ALD-material layer is etched or sputtered from the horizontal areas of the photoresist 4 and substrate material 5 , but remains on the sidewall of the photoresist feature 6
- FIG. 4 is a schematic which shows the status after the main etching step: substrate material is etched into the bulk 7 . This will end the first cycle. The same 3 steps then repeated certain amount of time to get the desired etch depth
- FIG. 5 is a schematic which shows the status after the second cycle.
- FIG. 6 is a schematic which shows the status after completion of the entire etch process: substrate feature is etched to the desired depth, sidewalls are still protected with SAM or ALD-material layer deposition
- FIG. 7 is a schematic which shows the status after optional SAM or ALD-material layer stripping from the sidewall of the feature.
- the present invention solves the problems associated with thickness and uniformity of sidewall passivation layers and enables successful high-aspect ratio anisotropic etch of micro and, especially, nanostructures.
- passivation polymer is deposited from the vapor phase in the form of self-assembled monolayer (SAM).
- SAM self-assembled monolayer
- FIG. 1 Self-assembled monolayers are arrays of aligned molecules, which have so called, a “head group”, used to attach molecule to the substrate using covalent or other bonding, organic “backbone”, and a “tail” group, which may have different properties (hydrophobic, hydrophilic, etc.
- Deposition process is self-limiting; it stops once the entire surface is covered with SAM, since the second layer of SAM can not be attached to the first. It means that SAM can not be accumulated on the sidewall and the thickness of such passivation layer on the sidewalls of the etched feature is the same through entire etch process. Uniformity of the deposition is excellent, since thickness is equal to the height of a single molecule (0.5-3 nm).
- FIG. 1 shows schematic representation of SAM, where ordered and self-aligned molecules are formed on the surface.
- SAM can be easily removed (sputtered) from the bottom of the feature using low energy ion bombardment, but SAM protects sidewalls of the feature from being etched, thus provides high anisotropy of the etch process.
- the current invention declares that Self-assembled Monolayers (SAMs) deposited on the sidewalls of the masking material and etched feature (trench, hole, etc.), which are not experiencing direct ion bombardment from Reactive Ion Etch plasma, are able to protect them from etch. Moreover, parts of SAM passivation layer damaged by grazing ion collisions or ion backscattering from the bottom of the trench can be “healed” with consecutive SAM deposition steps. Again, thickness of the “healed” layer still will not exceed one monolayer. Thus, SAMs can be successfully used as a sidewall passivation layers in anisotropic etch.
- SAMs Self-assembled Monolayers
- SAM deposition can be accomplished using a wide variety of organic precursors. Some examples of them are: Octadecyltrichlorosilane (OTS), Octyltrichlorosilane (OTCS), Dodecyltrichlorosilane (DDTCS), dimethyldichlorosilane (DDMS), tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (,FOTS), heptadecafluoro-1,1,2,2-tetrahydrodecyltrichlorosilane (FDTS), (tridecafluoro-1,1,2,2,-tetrahydrooctyl)trisdimethylamino silane (PF8TAS), (heptadecafluoro-1,1,2,2,-tetrahydrodecyl)tris-dimethylamino silane (PF10TAS).
- OTS Octadecyltrichlorosilane
- OCS
- Etch mask can be, for example, photoresist material.
- SAM passivation layer 3 which includes mask (photoresist) horizontal surfaces 4 , sidewalls of the patterned feature 6 , and exposed areas of the substrate 5 .
- thin inorganic films are used as a sidewall passivation layers.
- Such films can be deposited using well-known Atomic Layer Deposition techniques, wherein two vapors or gases are sequentially injected into the vacuum chamber and pumped from it, which builds a very conformal material over substrate surface, layer-by-layer.
- Very thin ALD deposited films can provide necessary passivation of sidewalls against etching species and, since ALD films are very thin, can be easily sputtered by directional ion beam of the biased plasma during etching step of the process.
- Example of such passivation film is aluminum oxide, which can be grown by sequential introduction to the chamber Trimethylaluminum (TMA) and water vapor or ozone gas.
- TMA Trimethylaluminum
- titanium oxide which can be grown by sequential introduction to the chamber titanium tetrachloride and water vapor.
- ALD deposition of these films at low temperatures (room to 100 C) can be done at rates about 1-5 ⁇ /cycle.
- plasma ions created by known reactive ion etching methods (RIE, ICP, TCP, etc.) in the presence of gasses (for example, Ar, He, etc.), directed towards the substrate surface, sputter or etch SAM or ALD-type passivation layer from the horizontal surfaces 4 of the mask material 2 and exposed area 5 of substrate material 1 .
- gasses for example, Ar, He, etc.
- Passivation layer 6 protects sidewall of the mask material 2 from being eroded during following sputtering and etching steps, thus helps to preserve critical dimension of the etched feature and enabling high aspect ratio etching process.
- removal of SAM passivation layer from the bottom of the etched feature is done UV exposure, preferably in an ambient of ozone or oxygen, or moisture.
- SAMs are efficiently etched by UV exposure in the presence of ozone.
- UV exposure can be implemented by providing a UV lamp or Laser and directing a light beams or collimated beam into the chamber toward the substrate material, preferably normal to the substrate surface.
- the third process step is an etching of exposed area 5 of the substrate material 1 , which creates (increases) feature depth 7 ( FIG. 4 ).
- the etching can be done any known dry etching process (RIE, ICP, TCP or other types of plasma etch process) with set of gasses appropriate for etching of specific substrate material.
- RIE dry etching process
- ICP ICP
- TCP plasma etch process
- gasses appropriate for etching of specific substrate material.
- perfluorinated gases SF 6 for oxides etch it is CHF 3 or CF 4 .
- etching of substrate material is performed with non-plasma etching means, for example, XeF 2 etch for Si or Ge, or anhydrous vapor HF etch for oxides.
- non-plasma etching means for example, XeF 2 etch for Si or Ge, or anhydrous vapor HF etch for oxides.
- the etch cycles include the above three process steps (passivation layer deposition, passivation layer etch from the horizontal surfaces, and etch of the substrate material) continues further until the substrate is etched to the desired depth ( FIG. 7 ).
- Remaining SAM can be etched from the sidewalls of the etched feature using oxygen plasma or ozone, or special wet stripping process ( FIG. 8 ).
- Remaining ALD-type passivation layer can be etched from the sidewalls of the etched feature using vapor or liquid etching processes.
- ALD oxide can be etched using HF vapor or liquid processes ( FIG. 8 ).
- the second and the third process steps are performed simultaneously, that is, removal of SAM or ALD-type passivation layer from the bottom of the etched feature is done simultaneously with material etch, using the same process.
- parameters of plasma etching process are modified to provide some directionality (anisotropy) of etch. Usually it is done by providing some bias to the plasma to increase ion directionality towards the substrate surface.
- SAM or ALD-type layer deposition is carried out without interruption, but sputtering or etching it from the bottom of the etched feature, and etching of substrate material—are performed in pulsing or cycling regime.
- SAM or ALD-precursor vapors are injected or flown into the vacuum chamber all the time, but etching gasses are injected or flown into the chamber during short periods with certain interruption time for deposition only process. This way SAM or ALD-type layer deposition process may create more continuous layer on the surface and better protect it from etching.
- an apparatus for performing the method described above comprising a chamber, means for depositing a passivation layer and means for etching a substrate and passivation layer.
- the means for etching the substrate and passivation layer may be provided by supplying one or more reactive gases or vapours to the chamber.
- Si material etching it can be SF 6 ClF 3 BrF 5 XeF 2 , etc.
- oxide material etching it can be CHF 3 , CF 4 or other etching gases or anhydrous HF vapor.
- SAM or ALD-type passivation layer sputtering can be achieved using biased plasma of Ar, He or other non-reactive gases.
- Specific embodiments may include further supplying RF energy (inductively or capacitively coupled via electrodes) or microwave energy to a plasma in the chamber.
- the means for depositing a passivation layer in the form of SAM or ALD-type layers may be provided by injecting vapours to the chamber by evaporation of liquid or solid chemical precursor, stored in a precursor supply cylinder or bottle.
- vapours can be carried from the precursor supply bottle with a help of carrier gas, for example, nitrogen.
- Step- 1 Deposition step: SAM passivation layer is deposited by flowing vapor of (heptadecafluoro-1,1,2,2,-tetrahydrodecyl)tris-dimethylamino silane into the chamber at a partial pressure of 100-500 mTorr for 5-30 seconds, and then evacuating chamber to the base pressure.
- Step-2 SAM etching from the bottom of the trench step: ICP plasma of SF 6 with addition of Ar (for example, ratio 2:1) and small plasma bias (electrode power 5-20W). 1-3 seconds of exposure to this plasma conditions should be enough to etch any SAM layer from horizontal surfaces.
- Ar for example, ratio 2:1
- small plasma bias electrode power 5-20W
- Step-3 Si material etch step: 5-10 seconds of SF 6 (100-200 sccm flow range)/Ar (30-80 sccm flow range) plasma, ICP coil power 600-900 W, bias 5-10 W.
- Steps 1-3 are repeated until desired feature depth is reached.
- SAM passivation layer is deposited during entire etch process by flowing vapor of (heptadecafluoro-1,1,2,2,-tetrahydrodecyl)tris-dimethylamino silane into the chamber at a partial pressure of 100-500 mTorr
- SAM etching from the bottom of the trench step and Si etching are carried out in a pulsing regime, 1-3 s ON, 3-5 s OFF. Parameters of this step: SF6 (100-200 sccm flow range)/Ar (30-80 sccm flow range) plasma, ICP power 600-900 W, bias 5-10 W.
- Step-1 Deposition step: Al 2 O 3 passivation layer is deposited by flowing vapor of Tetramethylaluminum (TMA) into the chamber for 0.5-1 s at a partial pressure of 50-200 mtorr, then evacuating the chamber to the base pressure, purging chamber with Nitrogen for 1-2 s, then injecting ozone gas for 0.5-1 s, evacuating chamber to base pressure and purging it with Nitrogen for 1-2 s. Then, by repeating this cycle 5 times, 7-10 ⁇ of Al 2 O 3 is grown on substrate surface.
- TMA Tetramethylaluminum
- Step-2 Al 2 O 3 sputtering from the bottom of the trench step: ICP plasma of SF 6 with addition of Ar (for example, ratio 2:1) and small plasma bias (electrode power 5-20 W). 1-3 seconds of exposure to this plasma conditions should be enough to sputter 10 ⁇ of Al 2 O 3 from horizontal surfaces.
- Step-3 Si material etch step: 5-10 seconds of SF 6 (100-200 sccm flow range)/Ar (30-80 sccm flow range) plasma, ICP coil power 600-900 W, bias 5-10 W.
- Steps 1-3 are repeated until desired feature depth is reached.
- Step-1 Deposition step: SAM passivation layer is deposited by flowing vapours of (heptadecafluoro-1,1,2,2,-tetrahydrodecyl)tris-dimethylamino silane into the chamber at a partial pressure of 100-500 mTorr for 5-30 s, and then evacuating chamber to the base pressure.
- Step-2 SAM etching from the bottom of the trench step: RIE plasma of Ar (partial pressure 200-500 mTorr) and small plasma bias (electrode power 10-20 W). 1-3 seconds of exposure to this plasma conditions should be enough to etch any SAM layer from horizontal surfaces.
- Step-3 Si material etch step: 5-10 seconds of XeF 2 (1.4 Torr partial pressure)
- Steps 1-3 are repeated until desired feature depth is reached.
- Step-1 Deposition step: Al 2 O 3 passivation layer is deposited by flowing vapor of Tetramethylaluminum (TMA) into the chamber for 0.5-1 s at a partial pressure of 50-200 mTorr, then evacuating chamber to the base pressure, purging chamber with Nitrogen for 1-2 s, then injecting ozone gas for 0.5-1 s, evacuating chamber to base pressure and purging it with Nitrogen for 1-2 s. Then, by repeating this cycle 5 times, 7-10 ⁇ of Al 2 O 3 is grown on substrate surface.
- TMA Tetramethylaluminum
- Step-2 Al 2 O 3 sputtering from the bottom of the trench step: RIE plasma of Ar (200-500 mTorr partial pressure) and small plasma bias (electrode power 10-20 W). 1-3 seconds of exposure to this plasma conditions should be enough to sputter 10 ⁇ of Al 2 O 3 from horizontal surfaces.
- Step-3 Silicon oxide material etch step: 5-10 seconds of anhydrous HF vapor HF/CH 3 OH) mixture 3-8 Torr partial pressure, 25:1 ratio).
- Steps 1-3 are repeated until desired feature depth is reached.
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